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Phosphorylated polyvinyl alcohol/perfluorosulfonic acid resin compound and ion exchange membrane

A technology of perfluorosulfonic acid resin and polyvinyl alcohol, applied in electrochemical generators, sustainable manufacturing/processing, final product manufacturing, etc., can solve the problems of low phosphoric acid content, limited proton exchange membrane performance, and difficulty in improving it. Achieve proper water absorption, excellent physical and mechanical properties, and prolong service life

Active Publication Date: 2021-09-24
国家电投集团氢能科技发展有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The disadvantage of this scheme is that the phosphoric acid content in the system is less and difficult to increase, which limits the further improvement of the performance of the proton exchange membrane

Method used

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  • Phosphorylated polyvinyl alcohol/perfluorosulfonic acid resin compound and ion exchange membrane
  • Phosphorylated polyvinyl alcohol/perfluorosulfonic acid resin compound and ion exchange membrane
  • Phosphorylated polyvinyl alcohol/perfluorosulfonic acid resin compound and ion exchange membrane

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Experimental program
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Effect test

preparation example Construction

[0043] According to the phosphorylated polyvinyl alcohol / perfluorosulfonic acid resin composite according to the embodiment of the present invention, the preparation method of the phosphorylated polyvinyl alcohol comprises:

[0044] a, polyvinyl alcohol is dissolved in a solvent to make a polyvinyl alcohol dispersion, wherein the solvent includes at least one of a high-boiling point organic solvent, water or a low-level aliphatic alcohol aqueous dispersion, wherein the high-boiling point The organic solvent is selected from at least one of ethylene glycol, propylene glycol, glycerol, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone ; The lower fatty alcohol is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol or isobutanol;

[0045] b. Adding a phosphoric acid functionalization reagent and a catalyst to the polyvinyl alcohol dispersion in step a to carry out a functionalization reaction, the reaction te...

Embodiment 1

[0064] Embodiment 1 prepares phosphorylated polyvinyl alcohol

[0065] Weigh 500g of polyvinyl alcohol and dissolve it in 10kg of deionized water at 90°C, add 1kg of concentrated phosphoric acid and 200g of urea, react at 140°C and 5MPa for 6h, add isopropanol to obtain a polymer precipitate, and then pass through isopropanol After washing, dry to obtain pure phosphorylated polyvinyl alcohol. The functionality of the phosphate group of the polymer was determined to be 19.8% by proton nuclear magnetic spectroscopy.

[0066] Soak 5 g of the solid product in 10 mL of ethanol, add a magnet to stir, centrifuge with a centrifuge after 30 days, and take the supernatant to determine the phosphoric acid content. The phosphorous content in the supernatant was measured using Thermo Fisher's Inductively Coupled Plasma Mass Spectrometer (ICP-MS), and the phosphoric acid content was calculated from the phosphorous content. The phosphorus content of the supernatant is only 8ppm, indicating...

Embodiment 2

[0067] Example 2 Preparation of highly functionalized phosphorylated polyvinyl alcohol

[0068] Weigh 50g of polyvinyl alcohol and dissolve it in 500mL of dimethyl sulfoxide at 120°C, add 100g of polyphosphoric acid without adding additional catalyst, and react with stirring at 160°C for 6h under the protection of nitrogen. The addition of methanol resulted in the precipitation of the polymer, which was dried to obtain pure phosphorylated polyvinyl alcohol. The functionality of the phosphate group of the polymer was determined to be 59.8% by proton nuclear magnetic spectroscopy. The method does not need to add additional catalyst, and the obtained product has a high degree of functionalization.

[0069] Soak 5 g of the solid product in 10 mL of ethanol, add a magnet to stir, centrifuge with a centrifuge after 30 days, and take the supernatant to determine the phosphoric acid content. The phosphorus content of the supernatant was measured by ICP-MS to be 12ppm, and the phosph...

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Abstract

The invention discloses a phosphorylated polyvinyl alcohol / perfluorinated sulfonic acid resin compound. The compound comprises the following components in percentage by mass: 0.1 to 77 percent of phosphorylated polyvinyl alcohol and 23 to 99.9 percent of perfluorinated sulfonic acid resin, and is prepared by adopting a blending method. When the phosphorylated polyvinyl alcohol / perfluorosulfonic acid resin compound is used for preparing an ion exchange membrane, the swelling and water absorption of the composite membrane can be limited, the proton transmission energy barrier is reduced, and the proton transmission capability of the composite membrane under high-temperature and low-humidity conditions is improved; as a result, the composite membrane has high ionic conductivity, high barrier property, excellent physical and mechanical properties and proper water absorption, and the non-covalent bond cross-linked structure also enables the membrane material to maintain the characteristic of recycling.

Description

technical field [0001] The invention belongs to the technical field of polymer materials, and specifically relates to a phosphorylated polyvinyl alcohol / perfluorosulfonic acid resin compound, and in particular to a phosphorylated polyvinyl alcohol / perfluorosulfonic acid resin ion exchange membrane. Background technique [0002] Perfluorosulfonic acid resin ion exchange membrane is the most widely used polymer membrane in low-temperature fuel cell technology. Currently, the commercially available perfluorosulfonic acid resin is non-crosslinked structure. Compared with crosslinked ion exchange resin, A clear advantage is the possibility of dissolution recovery by solvent. Polyhydric polymers, synthetic polymers such as polyvinyl alcohol (PVA), polyethylene glycol, and natural polymers such as cellulose, hemicellulose, lignin, chitosan, sodium alginate, and lignin are common Hydrophilic polymers that can be dissolved or dispersed in water or hydroalcoholic solvents. Functiona...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08L27/22C08L29/04H01M8/1039H01M8/1048
CPCC08L27/22C08L29/04H01M8/1039H01M8/1048C08L2203/20Y02P70/50
Inventor 周朝毅张泽天刘昊李道喜李丹张亚欢鹿传睿董天都
Owner 国家电投集团氢能科技发展有限公司
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